Azo-dyestuffs



Patented Dec. 29, 1936 UNITED STATES AZO-DYESTUFFS Grald Bonhote, Basel,

Riehen, Switzerland,

and Carl Apotheker, assignors to Society of Chemical Industry in Basie, Basel, Switzerland No Drawing. Application May 20, 1936, Serial No. 80,907. In Switzerland May 22, 1935 11 Claims.

According to this invention new azo-dyestuifs are obtained'by combining with a coupling component, particularly with a coupling component which couples due to the presence of an OH- group, a diazotized amino-azo compound corresponding with the general formulawherein R1 and R2 representaromatic radicals selected from thegroup consisting of aromatic radicals of the benzene and naphthalene series and wherein there is present in ortho-position to the diazo-group a group OR, B representing an etherified hydroxy-alkyl radical.

In this manner there may be produced dyestuffs which correspond to the general formula wherein R1 and R2 stand for aromatic nuclei selected from the group of the aromatic nuclei of the benzene and naphthalene series, R3 stands for the radical of a coupling component which couples due to the presence of an OH-group, and wherein the aromatic nucleus R2 carries an OR4-group in ortho-position to the group N=N-R3, R4 representing an etherified hydroxy-alkyl radical, which dyestuffs are useful for various purposes. If there are used sulfonate coupling components there are obtained dyestuffs which may be useful for dyeing wool or cotton. By usingunsulionated coupling components there are obtained insoluble dyestuffs which may be used as lakes or pigments or for other purposes. Among these insoluble dyestufis those are of particular value which are obtained by combining a diazo-component of the foregoing formula with an arylide of an aromatic orthohydroxy-carboxylic acid which couples with diazo-compounds in ortho-position to the hydroxyl group. When produced on suitable substrata, for example on textile material, these dyestuffs yield inter alia orange, brown, Bordeaux to violet, blue and black tints which may be distinguished by excellent properties of fastness. There are also valuable dyestuffs obtained from other coupling components, such as those containing a methylene group capable of coupling.

Among the diazo-components which are espe-' cially suitable for use in the present invention there may be named quite generally the monoazo-dyestufis which are obtainable by combining the diazo-compounds of aniline, the three toluidines, the xylidines, the three'nitranilines, the substitution products of these diazo-comv ponents containing in the nucleus halogen or nitro-groups, aand'c-naphthylamine, the anisidines and phenetidines, such as orthoor paraanisidlne, or orthoor paraphenetidine, substitution products of these diazo-components con- Q taining nuclear halogen or nitro-groups, l-amino- 2-methoxy-naphthalene and so on, with coupling components such as the w-methoxyethyl ether of Z-amino-I-hydroxybenzene, the w-ethoxyethyl ether of 2-amino-1-hydroxybenzene, the w-methoxyethyl-ether of 2-amino-5-methyll-hydroxybenzene or of 2-amino-5-methoxyor -5-ethoxy-l-hydroxybenzene, th e w-methoxybutylether of 2-amino-1-hydroxybenzene, the wmethoxyethyl ether of l-amino-Z-hydroxynaphthalene and so on. Similar results are for example obtained with the w-acetyl-hydroxy-ethyl ester of 2-amino-1-hydroxybenzene which has a similar constitution.

The present invention is however not limited to azo-dyestufis containing w-methoxyethyl and w-ethoxyethyl groups. According to the present process there may also be produced such dyestuffs which contain instead of w-methoxyethyl groups for example w-ethoxybutyl, o-ethoxypropyl, w-ethoxyamyl groups, or the longer radical may be linked to that oxygen atom which is bound to the aromatic nucleus, in which case the dyestuffs of the present invention contain for example w-amylhydroxyethyl groups.

With regard to the coupling components for making the dyestuffs in accordance with the present invention, it has already been pointed out that above all such components may be used successfully which due to the presence of an OH-group are capable of coupling. This expression comprises not only coupling components of the kind of the hydroxybenzenes, hydroxynaphthenes, hydroxyanthracenes and the like, but also the coupling components containing the -CHzCO-groups, such as pyrazolones and derivatives of the acetoacetic esters, such as acetoacetic anilide and the like, which, as is known, react with diazo compounds for the reason because the CO-group is capable of being converted into the enol form, that is to say the group CH2-C=O reacts as OH CH=-group As coupling components there may thus be named the various hydroxynaphthalenes and amino hydroxynaphthalenes and their sulfonic acids, as

well as N-acyl derivatives of these substances,

and 1:2:5z4, the 2,3-hydroxynaphthoic acid, the 6-bromo-2,3-hydroxynaphthoic acid, the 2,3-an- 2 thracene-hydroxycarboxylic acid, the 2,3-hydroxycarbazol-carboxylic acid, the benzo-Z-hydroxycarbazol-3-carboxylic acid and the like, wherein the arylide radical is represented by radicals of aromatic monoand diamines, such as the radicals of aniline, the toluidines, the chlorotoluidines, meta-nitraniline, aand enaphthylamine, para-phenylenediamine, benzidine, tolidine, dianisidine and the like, there being used in the case of diamines preferably such arylides which contain twice the radical of the aromatic ortho-hydroxycarboxylic acid. Besides these coupling components, as. indicated above, there may also be employed still other components, such as pyrazolone sulfonic acids and derivatives of aceto-acetic esters, such as di- (aceto-acetyl) -ortho ortho-tolidine, as well as terephthaloyl-bis-acetic acid anilide, benzoyl acetic acid, ortho-chloranilide, barbituric acid and so on.

Among the dyestufis of the present invention those are particularly valuable which correspond with the general formulawherein R1 and R2 stand for aromatic nuclei of the benzene series which carry neither sulfogroups nor carboxylic groups, wherein the aromatic radical R2 carries an O-CI-Iz-CH2-O-CHa-group in ortho-position to the radicaland wherein ac stands for an unsulfonated and non-carboxylated aromatic nucleus selected from the group consisting of the aromatic nuclei of the benzene .and naphthalene series, which products are dark powders insoluble in water, but soluble in pyridine to wine-red solutions and in sulfuric acid to green solutions, and which when produced on vegetable fibers or viscose artificial silk, dye the same fast Bordeaux red and violet to black tints.

The following examples illustrate the invention:--

Example 1 27.1 parts by weight of 4-amino-3-(w-methoxy)-ethoxy-1,1-azobenzene are diazotized in the usual manner and introduced into a solution of 26.3 parts of 2,3-hydroxynaphthoic acid anilide, 50 parts of caustic soda solution of 30 per cent strength and 30 parts of anhydrous sodium carbonate in 2000 parts of water. The dyestufi of the formula- $11. i'm JJH:

which is formed separates at once as a Bordeaux red precipitate which is filtered and dried. It dissolves in sulfuric acid to a. green solution and in pyridine to a wine-red solution.

Example 2 The dyestuff if produced in substance dissolves in sulfuric acid to a green solution and in pyridine to a wine-red solution.

Similar shades are obtained, for example, if, as the coupling component, there is used the fi-naphthalide or the 2-methoxyanilide of 2,3- hydroxy-naphthoic acid.

Example 3 The diazo solution is allowed to run into a solution consisting of 34.8 parts of 2-hydroxynaphthalene-3,6-disulfonic acid, 348 parts of water and 21.2 parts of sodium carbonate.

The dyestufi it" produced in substance dissolves in sulfuric acid to a green solution and in pyridine to a. wine-red solution.

Similar currant tints are obtained, for example,

5 if Y y P l is A red-brown precipitate separates at once used as coupling component. which is then filtered and dried. There is thus 311111131 P 1 are obtamed m dyfemg Place obtained a red-brown powder which dissolves goods and m prmtingin water and pyridine to wine-red solutions and Emmflle 4 in concentrated sulfuric acid to a blue solution. 10 30.75 parts of 4-amino-3-(w-methoxy)-ethoxy- It dyes W001 from an acid bath Bordeaux red 1,1'-azobenzene-chlorohydrate are introduced, tints. The dyestuif from 1-benzoylamino-8-hywhile stirring, into a mixture of 30 parts of hydroxynaphthalene-3,6-disulfonic acid dyes wool drochloric acid of 30 per cent. strength, 20 parts garnet red tint of water and parts Oflce a d t e th t The following table displays further examples 15 s d a t e y iIItIOdU-Cmg y drops a SOIIltIOn f of products obtainable according to the process of 7.2 parts of sodium nitrite in 15 parts of water. the present invention:-

Diazotizing components 7 Coupling components gg figggg Colorinsulfuricacid gf f g 20 20 2 s-hydroxynaphthoic acid (1) 4 -amino-5- (w -methoxy) -ethoxy-4 4 -methylanilide Currant-Violet Red-violet.

mtro-1,1-azobenzene. s (2) Do- 4-chloranilide Do. (3) Do 1-naphthy1amide Do. (4) Do 2-nephthylamide Do 25 (5) Do 4-methoxyanilide D (6) Do. ethoxyanilidenu Do. (7) Do 2,5'-d methoxyenilide Do. (8) D o 2,4'-d1methpg y-5-chloroanilide Do. (9) 4-amno-5- (w 4-eth0xyan1l1de Wine-red.

820 61129118. (10) Do 4-m thoxyanilide B1ue-Bordeaux D0. (11)-4-amino-5 -(w-methoxy)-ethoxy-2- 1-naphthy1amide Currant-Violet" Do. 3

chloro-4-n1tro-1,l-ezobenzene. (12) Do 2-naphthylamide Red-violet. 13) 4-methoxyanilide Do; (14) 4-ethoxyani1ide D0. (:15) gigiiimethlogyanilide Do. 6 -c oroami e D (17) 4-amino-5-(w-meth0xy)-6th0xy-2,4'-di0hl0- 1'-naphthylamide Winegred. v

ro-1,1-azobenzene.

(18) Do 4'-methoxyanilide Do.

519; 30 gjg j Do. 20 o -me y -me oxyanilide. Do. (21) 4-amigo-5-w-methoxy)-ethoxy-2-chloro-1,1'- 2-methyl-4-ehloroanilide Do.

820 ED29116- (22; Do- Anilide 4 (23 Do 4-ch1oroani1ide (24) Do-- 1'-naphthylamide (25; Do 2-naphthylamide- (26 Do 4-methoxyanilide (27) Do 2-methoxyanilide (28) Do 4'-methylanili (29) Do 4-ethoxyanilide d 4,5 (30) 4-amoige gmethoxy)-ethoxy-4-n1tro-1,1- 4-methoxyanilide. o tiol t az nz (3 g gj-g q do (32 0 Lme OXY '0 OIOfilll d0 (33; 4 amino 5 (w methoxy) ethoxy 3- 2',4-dimethoxy-5-chloroanilide Bordeaux-garnet..

chloro-l,1'-azobenzene. (34) Do 2-methy1-4-methoxyanilide Egg; gigg g g -9 OXYB 8 (37) 4 w ethoxy) -ethoxy 3- 4-ch10rom1ilirl4i chloro-1,l-azobenzene. (38) Do l-naphthylamide 4'-methoxyanilide.- 4-methylanilide.. l-naphthylamide 2'-naphthylaznide 4'-methoxyanilide- 2-methoxyanilido-- 4-ethoxyanilide 7,8- benzocarbazole 3'-hydroxy-2- carbonyl-p-anisidide. 7,8 btelnzlocarbagle 3- llfiYil'OXY -2- me y-p-me oxyam 6. (48) 4 -fi1mim; 5 (Li; mgtioxy) ethoxy 2- di-(acetylaceto)-o, o-tolidine Gold-orange 0 010- -8Z0 91118 (49) 4-ziif ino--(w-methoxy)-ethoxy-2-chloro- Z-gaygaoxygarbug?-3-carboxylic Dark brown Gieen with blue Wine-red.

4120 61126116. 01 -0 cram e. lnge. (50) D 7,8-benzocarbazole-3-hydroxy-2- Black do Blue.

carbonyl-p-methoxyamlide. (51) Do 7,8-benzocarbaz01e-3-hydroxy-2- do do Do.

methyl-p-methoxyanilide. (52) 4-amino-5-(w-methoxy)-ethoxy-2-chloro-4- di-(1-hydroxy-4-methyl-2-benzoy1) Brown do Reddishnitro-1,1-azobenzene benzidme. brown. (53) Do GI-(I-IIYQiIQXY-i-HlflthYI-Z- BHZOYD do do Brown 'amsidme. with red inge. (54) Do di-(l hydroxy-tmethyla-benzoyl) Dark brown do.. Do.

fohdme. 10

(56) Do d1-(acetylaceto)-o,o-t0hdme Orange-brown- Bl ue with violet Orange,

mge. (56) Do 2,3 -l l sgro y acagbe cgg-carboxylic Brown Bl ne with green Wine-red.

Cl -(5 1'0 111 111 e. (57) Do 7,8-benzocarbazole-3-hydroxy-2- Black d o Greanish.

carbonyl-p-methoxyanilide. (58) Do 7,8-banzocarbazole-3-l1ydroxy-2- do Blue Do. 7 methyl-p-methoxyamlide.

What we claim is:.-, 1. The dyestuffsof the general formula- R1-N=NR2' =N- R3 wherein R1 and R2 stand for aromatic nuclei selected from the group of the aromatic nuclei of the benzene and naphthalene series, R3 stands for the radical of a coupling component which couples due to the presence of an OH-group,-and wherein the aromatic nucleus R2 carries an: O-R4-group in ortho-position to the group N=NR3, R4 representing an etherified hydroxy-alkyl radical, which products are dark powders dissolving in sulfuric acid to yellow to red, to violet and green solutions, and in pyridine to yellow to red, to violet and blue solutions, which dyestuffs when produced on the fiber dye the same fast orange to brown, to garnet, to violet and black tints.

. 2,.The dyestuffs of the general formula-- wherein R1 and R2 stand for aromatic nuclei selected from the groupof the aromatic nuclei of thebenzene and'naphthalene series, R3 stands for the radical of an arylide of an ortho-hydroxycarboxylic acid selected from the group consisting of the ortho-hydroxycarboxylic acids of the benzene and naphthalene series which couples with diazo compounds in ortho-position to the OH-group, and wherein the aromatic nucleus R2 carries an 0R4-group in ortho-position to the group N=NR3, R4 representing an etherified hydroxy-alkyl radical, which products do not contain substituents of the group consisting of sulfo and carboxylic groups and are dark powders insoluble in water, but dissolving in sulfuric acid to yellow to red, to violet and green solutions, and in pyridine to yellow to red, to violet and blue solutions, which dyestuffs when produced on cotton dye the same fast orange to brown to garnet to violet and black tints.

3. The dyestfis of the general formulaF wherein R1 and R2 stand for aromatic nuclei selected from the group of the aromatic nuclei of the benzene and naphthalene series, R3 stands for the radical of an arylide of the 2,3-hydroxynaphthoic acid, and wherein the aromatic nucleus R2 carries an O-Rr-group in ortho-position to the group N=NR3, R4 representing an etherified hydroxy-alkyl radical, which products do not contain substituents of the group consisting of sulfo and carboxylic groups and are dark powders insoluble in water, but dissolving in sulfuric acid to green solutions, and in pyridine to wine-red to red-violet solutions, which dyestufis when produced on cotton dye the same fast garnet to currant-violet tints.

4. The dyestuffs of the general formulawherein R1 and R2 stand for aromatic nuclei of the benzene series, R3 stands for the radical of an arylide of the 2,3-hydroxynaphthoic acid, and wherein the aromatic nucleus R2 carries an OR4-group in ortho-position to the group N=NR3, R4 representing an etherified hydroxy-alkyl radical, which products do not contain substituents of the group consisting of sulfo and carboxylic groups and are dark powders insoluble in Water, but dissolving in sulfuric acid to green solutions, and in pyridine to wine-red to red-violet solutions, which dyestuffs when produced on cotton dye the same fast garnet to currant-violet tints.

5. The dyestufis of the general formula- R1N=N-R2-N=NR3 wherein R1 and R2 stand for aromatic nuclei of the benzene series, R3 stands for the radical of an arylide of the 2,3-hydroxynaphthoic acid, and wherein the aromatic nucleus R2 carries a CH2CH2OCH3-group group -N=NRs, which products do not contain substituents of the group consisting of sulfo and carboxylic groups and are dark powders insolublein water, but dissolving in sulfuric acid'to green solutions, and in pyridine to wine-red to red-violet solutions, which dyestuffs when produced on cotton dye the same fast garnet to ourrant-violet tints.

6. The dyestuifsof the general formula o H (i=0 6H: BIG-R ts, (IF-CH:

l +H2 SEN-R CH:

wherein R stands for an aryl nucleus selected from the group consisting of aryl nuclei of the benzene and. naphthalene series, which products are dark powders insoluble in water, but dissolving in sulfuric acid to green solution and in pyridine to wine-red solutions, which dyestuffs when produced on the vegetable fiber dye the same fast Bordeaux tints.

.10 in ortho-position to the which dyestufi when produced on the vegetable 15 fiber dyes the same fast current-violet tints.

' 10. The azo-dyestufi of the formulawhich dyestufi when produced on the vegetable fiber dyes the same fast Bordeaux tints.

11. The azo-dyestuff of the formula,-

. I H lg- 1 0 (311: NH E O-GHa GERALD BONHOTE.

CARL APOTHEKER. 25 

